WO1986007600A1 - Composition d'elastomere thermoplastique - Google Patents

Composition d'elastomere thermoplastique Download PDF

Info

Publication number
WO1986007600A1
WO1986007600A1 PCT/US1986/001306 US8601306W WO8607600A1 WO 1986007600 A1 WO1986007600 A1 WO 1986007600A1 US 8601306 W US8601306 W US 8601306W WO 8607600 A1 WO8607600 A1 WO 8607600A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
weight
component
parts
rubber
Prior art date
Application number
PCT/US1986/001306
Other languages
English (en)
Inventor
Eiji Sezaki
Takashi Mikami
Tsuyoshi Kanai
Toshio Yoshida
Kikuo Tanaka
Masaaki Saito
Original Assignee
Exxon Chemical Patents Inc.
Tonen Sekiyukagaku K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP13167185A external-priority patent/JPS61291639A/ja
Priority claimed from JP60131670A external-priority patent/JPS61291638A/ja
Application filed by Exxon Chemical Patents Inc., Tonen Sekiyukagaku K.K. filed Critical Exxon Chemical Patents Inc.
Priority to DE8686904526T priority Critical patent/DE3673973D1/de
Priority to BR8606735A priority patent/BR8606735A/pt
Priority to KR1019870700143A priority patent/KR920010646B1/ko
Publication of WO1986007600A1 publication Critical patent/WO1986007600A1/fr
Priority to NO870647A priority patent/NO870647D0/no
Priority to DK084687A priority patent/DK84687A/da

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C08L23/283—Halogenated homo- or copolymers of iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • the present invention relates to a thermoplastic elastomer composition.
  • thermoplastic elastomer compositions which are formed by partially crosslinkrng a composition composed of a polyolefin and a rubber component in the presence of a crosslinking agent.
  • the crosslinking agent used in the production of these compositions is mainly an organic peroxide, sulfur, or a vulcanization accelerator for sulfur-cured rubber.
  • the crosslinking agent of organic peroxide has some disadvantages. It is so reactive that it is difficult to properly control the degree of crosslinking. It brings about the scission of molecules simultaneously with crosslinking, deteriorating the properties of a composition or increasing the melt index of a polyolefin. This in turn adversely affects the drawdown of the melt at the time of molding and causes the surface roughening of the moldings due to partial gelling. In addition, free radicals induced by an organic peroxide remain in the moldings to aggravate the thermal stability of the moldings. On the other hand, a crosslinking of sulfur forms the S-S linkage which adversely affects the thermal stability.
  • thermoplastic elastomer composition which comprises (A) 5 to 40 wt% of polyisobutylene and/or butyl rubber, (B) 30 to 90 wt% of e thylene-propylene copolymer rubber and/or ethylene- propylene-non-conjugated diene terpolymer rubber, and (C) 5 to 40 wt % of polyolefin resin.
  • the crosslinking agent used in this composition is substantially an organic peroxide, and the crosslinking of the composition takes place mainly in component (B). Therefore, the miscibility of the components and the oil resistance were less than perfect.
  • the composition is a thermoplastic elastomer composition superior in moldability, heat resistance, miscibility, and where nitrile rubber is included in the composition, oil resistance, in which there is no molecular scission and the olefin copolymer rubber is not substantially crosslinked.
  • the present inventors conducted a series of experiments which led to the finding that when a composition of polyolefin such as polypropylene, olefin copolymer rubber, modified polyolefin, halogenated butyl rubber and optionally, nitrile rubber, is subjected to crosslinking with a crosslinking agent of a metal oxide and/or a metal chloride, the halogenated butyl rubber alone is selectively cross- linked.
  • polyolefin such as polypropylene, olefin copolymer rubber, modified polyolefin, halogenated butyl rubber and optionally, nitrile rubber
  • thermoplastic elastomer composition and process comprising (A) 10 to 90 parts by weight of crystalline polyolefin such as polypropylene, (B) 10 to 90 parts by weight of halogenated butyl rubber (with the total amount of (A) and (B) being 100 parts by weight), (C) 10 to 120 parts by weight of olefin copolymer rubber, (D) 1 to 90 parts by weight of modified polyolefin, and optionally (E) 2 to 50 parts by weight of nitrile rubber, said composition being partially crosslinked in the presence of a crosslinking agent of a metal oxide and/or a metal chloride.
  • crystalline polyolefin such as polypropylene
  • B 10 to 90 parts by weight of halogenated butyl rubber (with the total amount of (A) and (B) being 100 parts by weight)
  • C) 10 to 120 parts by weight of olefin copolymer rubber (D) 1 to 90 parts by weight of modified polyolefin, and optionally (
  • This component comprises a homopolymer of propylene or a copolymer of propylene with an alpha-olefin such as ethylene, 1-butene, 1-hexene, and 4-methyl-1-pentene. It has a melt flow rate (abbreviated as MFR hereinafter) of 0.3 to 60 g/10 min, preferably 1 to 40 g/10 min, and more preferably 3 to 30 g/10 min. (This component is designated as component A hereinafter.)
  • Component A has the highest melting point among polyolefins; and it contributes to an improvement in heat resistance and mechanical strength.
  • This component denotes a halogenated isobutylene-isoprene copolymer rubber.
  • halogen examples include chlorine and bromine.
  • the content of halogen is usually 0.5 to 4.0 wt%.
  • Component B should preferably have a Mooney viscosity of 30 to 100 ML 1+8 (100°C) and a degree of unsaturation of 0.5 to 4.0 mol%.
  • Component B is a rubber capable of crosslinking with a metal oxide or metal chloride. It is dispersed in the form, of crosslinked rubber in the composition. It imparts heat resistance, oil resistance, vibration absorption, gas impermeability, and slip resistance to the composition.
  • This component includes copolymer rubbers each composed of two or more monoolefins such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene (typically ethylene-propylene copolymer rubber) and copolymer rubbers each composed of two of the above-mentioned monoolefins (preferably ethylene and propylene) and a non-conjugated diolefin such as dicyclopentadiene, 1,4-hexadiene, cycloocta- diene, methylenenorbornene, and ethylidenenorbornene, or a conjugated diolefin such as butadiene and isorprene.
  • monoolefins such as ethylene, propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene
  • copolymer rubbers each composed of two of the above-mentioned monoolefins (preferably ethylene
  • Component C should preferably have a Mooney viscosity of 5 to 300 ML 1+8 (127°C), an iodine value up to 30, and an ethylene content of 35 to 85 wt%.
  • component C is present in the form of non-crosslinked rubber. It imparts the molding flowability to the composition and works as a binder at the phase boundary between component A and component B. It also contributes to an improvement in tensile strength and elongation of the composition.
  • This component includes those which are formed by adding an unsaturated carboxylic acid or a derivative thereof to a polyolefin. (It is designated as component D hereinafter.)
  • polystyrene resin examples include homopoly- mers of alpha-olefin such as ethylene, propylene, 1-butene, 1-hexene, and 4-methy1-1-entene, and copolymers of ethylene with one or more a lpha-olefins.
  • alpha-olefin such as ethylene, propylene, 1-butene, 1-hexene, and 4-methy1-1-entene
  • copolymers of ethylene with one or more a lpha-olefins Preferable among the polyolefins are low-density polyethylene, linear low-density polyethylene, medium- and high-density polyethylene, polypropylene, and propy lene-ethylene random or block copolymers.
  • Examples of the unsaturated carboxylic acid include maleic acid, endo-bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, itaconic acid, fumaric acid, acrylic acid, and methacrylic acid.
  • Examples of their derivatives include acid anhydrides, acid amides, and esters.
  • the reaction of an unsaturated carboxylic acid or a derivative thereof with a polyolefin may be accomplished by any known method.
  • the reaction may be accomplished by adding a reaction initiator such as organic peroxide to a mixture of polyolefin and an unsaturated carboxylic acid or a derivative thereof, and then melt-mixing the resulting mixture.
  • the amount of an unsaturated carboxylic acid or a derivative thereof to be added to a polyolfin should preferably be 0.02 to 2 wt%.
  • Component D may contain an olefin copolymer rubber such as the above-mentioned component C (which has a Mooney viscosity of 5 to 300 ML 1+8 (127°C), an iodine value up to 30, and an ethylene content of 35 to 85 wt% .) or a polyisobutylene having a density of 0.91 to 0.93 g/cc and a molecular weight of 60,000 to 135,000 (measured according to Staudinger method).
  • an olefin copolymer rubber such as the above-mentioned component C (which has a Mooney viscosity of 5 to 300 ML 1+8 (127°C), an iodine value up to 30, and an ethylene content of 35 to 85 wt% .) or a polyisobutylene having a density of 0.91 to 0.93 g/cc and a molecular weight of 60,000 to 135,000 (measured according to Staudinger method).
  • the mixture should preferably comprise 10 to 90 wt% of polyolefin, 90 to 10 wt% of olefin rubber, and the amount of acid should preferably be 0.02 to 2 wt%.
  • Component D functions as a binder which makes the individual components in the composition miscible with one another, and it also contributes to an improvement in mechanical strength of the composition.
  • acrylonitrile-butadiene copolymer rubber referred to as component E hereinafter.
  • the preferred nitrile rubber contains 20 to 50 wt% of acrylonitrile and has a Mooney viscosity of 15 to 150 ML 1+8 (100°C).
  • Component E contributes to an improvement in the oil resistance of the composition.
  • metal oxide crosslinking agent examples include zinc oxide, magnesium oxide, lead oxide, and calcium oxide, with zinc oxide being preferable.
  • metal chloride crosslinking agent examples include zinc chloride and tin chloride. It should preferably be used in combination with magnesium oxide to capture free halogen which otherwise corrodes the mold and the like.
  • the crosslinking agent should be used in an amount of 0.2 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of component A, component B, component C, component D, and when used, component E.
  • the composition may be incoprorated with a mineral oil softener in an amount of up to 150 parts by weight per 100 parts by weight in total of component A and component B.
  • the softener include naphthenic, paraffinic, and aromatic rubber process oils and mineral oils which are high-boiling fractions of petroleum.
  • the composition may include, as required, stabilizers such as antioxidant, ultraviolet light absorber, and metal deactivat ⁇ r; additives such as slip agent, antistatic agent, electric property improver, flame retardant, processing aid, and pigment; and inorganic fillers such as talc, calcium carbonate, barium sulfate-j mica, and calcium silicate.
  • the compounding ratio of components A, B, C, D and E useful in this invention include:
  • Component A 10 to 90 parts by weight, preferably 20 to 70 parts by weight.
  • Component B 10 to 90 parts by weight, preferably 30 to 80 parts by weight. (The amounts of components A and B are selected so that their total is 100 parts by weight.)
  • Component C 10 to 120 parts by weight, preferably 10 to 50 parts by weight.
  • Component D 1 to 90 parts by weight, preferably 5 to 50 parts by weight.
  • Component E 2 to 50 parts by weight, preferably 5 to 30 parts by weight.
  • the composition With component A less than 210 parts by weight, the composition is poor in mechanical strength and heat resistance. On the other hand, with component A in excess of 90 parts by weight, the composition is poor in elastomeric properties due to high hardness and high compression set.
  • the composition With component C less than 10 parts by weight, the composition is poor in flexibility and molding flowability, and also in miscibility of component A and component B. On the other hand, with component C in excess of 120 parts by weight, the composition has a low mechanical strength and a high compression set.
  • component D With component D less than 1 part by weight, the composition is poor in mechanical strength due to insufficient miscibility of individual components. On the other hand, if the amount of component D exceeds 90 parts by weight, its effect reaches a plateau and it is wasteful.
  • component E When component E is included if it is less than 2 parts by weight, the composition is not improved in oil resistance. On the other hand, with component E in excess of 50 parts by weight, the composition is poor in flowability.
  • the composition of this invention is prepared by bringing components A, B, C, D, and, when used, E, and a crosslinking agent and other optional components into contact with one another in the molten state.
  • the components excluding a crosslinking agent are melted and mixed preliminarily for 1 to 10 minutes, and then a crosslinking agent is added and mixing is continued for 1 to 30 minutes in the molten state.
  • component B alone selectively undergoes crosslinking to give the composition which achieves the object of the invention.
  • the melting and mixing may be. accomplished with a commonly used pressurized kneader, Banbury mixer, or screw extruder.
  • composition of this invention is superior in mechanical strength, heat resistance, moldability, and oil resistance because the components thereof are highly miscible with one another. It is produced without using a difficult to control organic peroxide.
  • the crosslinking agent used in this invention is so thermally stable that it is possible to control the degree of crosslinking as desired.
  • the composition of the invention has well-balanced flexibility, strength, and heat resistance, and also has good moldability; therefore, it is suitable as a raw material for auto parts such as, rack/pinion, boots, hoses, side moldings, spoilers, bumpers, and the like, which are readily molded by the conventional molding method such as blow molding, extrusion molding, and injection molding.
  • auto parts such as, rack/pinion, boots, hoses, side moldings, spoilers, bumpers, and the like, which are readily molded by the conventional molding method such as blow molding, extrusion molding, and injection molding.
  • MFR 315 K7210 (load 2.16 kg, 230°C)
  • MLMFR JIS K7210 (load 10 kg, 230°C)
  • Tensile strength at break and elongation JIS K6301
  • Hardness by spring .type tester JIS K6301, Type A (6)
  • Compression set JIS K6301, 70°C x 22 hours, 25% compression
  • Heat resistance Expressed in terms of the ratio of the elongation (%) measured before heat aging to the elongation ( % ) measured after heat aging at 150°C in an oven for 600 hours. 70% and higher is indicated by “o", 50% to less than 70% is indica'ted by " ⁇ ", and less than 50% is indicated by"x".
  • Oil resistance JIS K6310. Rated according to swelling that takes place after immersion in s JIS No. 3 oil. ⁇ : less than 50%, o: 50 to less than 100%, ⁇ : 100 to less than 200%, x: more than 200%.
  • Component A Propy lene-ethylene block copolymer
  • Component B Chlorinated isobutylene-isoprene copolymer rubber (Mooney viscosity: 50 ML 1+8 (100°C), chlorine content: 1%, and degree of unsat urat ion : 2 mol%. Referred to as “ClIIR” hereinafter.) Isobutylene-isoprene copolymer rubber (Exxon Butyl 268, a product of Exxon Chemical Company, referred to as "IIR” hereinafter.)
  • Component C Ethyl ene-propylene-ethylidenenor- bornene copolymer rubber (Mooney viscosity : 230 ML 1 + 8 ( 1 27 ° C ) , i o d i n e v a l u e : 1 8 , an d e t h y l e n e content: 60%. Referred to as “EPDM” hereinafter.) Ethylene-propylene rubber (Mooney viscosity: 25 ML 1+8 (127°C), and ethylene content: 40%. Referred to as "EPM” hereinafter.)
  • Component D PP block (MFR: 10 g/10 min, ethylene content: 7%) modified with endobicyclo-[2.2.1]-5-heptene-2,3- dicarboxylic anhydride (amount of the acid added: 0.3%, referred to a "CMPP” hereinafter.)
  • High-density polyethylene density: .0.950 g/cc, MI: 10 g/10 min, referred to as “HDPE” hereinafter.
  • MA maleic anhydride
  • Linear low-density polyethylene (density: 0.925 g/cc, MI: 5 g/10 min, referred to as "LLDPE” hereinafter) modified with MA (amount of the acid added: 0.3%, referred to as "CMLLDPE” hereinafter.)
  • a mixture of 90% of LLDPE density :0.925 g/cc, MI
  • CMPD 10 CMEPM 90 A mixture of 10% of HDPE (density: 0.950 g/cc, MI: 8.0 g/10 min) and 90% of EPM (Mooney viscosity: 25 ML 1+8 (127°C), and ethylene content: 70%.) modified with MA (amount of the acid: 0.3%, referred to as CMPD 10 CMEPM 90).
  • Component E Zinc oxide, zinc chloride, 2,5-di-(tbutylperoxy)-hexyne-3 (crosslinking agent, referred to as “P.O” hereinafter), and magnesium oxide (halogen capturing agent).
  • Component F Napthenic and paraffinic mixed process oil (referred to as “softener” hereinafter), and talc (having an average particle diameter of 4 um).
  • component E crosslinking agent
  • Table 1 shows the characteristic properties of each composition.
  • Example 5 The composition in Example 5 was examined for the degree of crosslinking.
  • the amount of insoluble matter (excluding talc) was 13.0%, and the infrared absorption spectrum, indicated that crosslinking took place only in component B.
  • Component A Propylene-ethylene block copolymer (density: 0.90 g/cc, MFR: 3.0 g/10 min, and ethylene content: 7%. Referred to as “PP block” hereinafter).
  • Component B Chlorinated isobutylene-isoprene copolymer rubber (Mooney viscosity: 50 ML 1+8 (100°C), chlorine content: 1%, and degree of unsaturation: 2 mol%. Referred to as “ClIIR” hereinafter.)
  • Component C Ethylene-propylene-ethylidenenor- bornen copolymer rubber (Mooney viscosity: 230 ML 1+8 (127°C), iodine value: 18, and ethylene content: 60%. Referred to as “EPDM” hereinafter.) Ethylene-propylene rubber (Mooney viscosity: 25 ML 1+8 (127°C), and ethylene content: 40%. Referred to as "EPM” hereinafter.)
  • Component D PP block (MFR: 10 g/10 min, ethylene content: 7%) modified with endobicyclo-[2.2.1]-5-heptene-2,3- dicarboxylic anhydride (amount of the acid added: 0.3%, referred to as "CMPP" hereinafter.)
  • CMPP endobicyclo-[2.2.1]-5-heptene-2,3- dicarboxylic anhydride
  • a mixture of 10% of HDPE density: 0.950g/cc, MI: 8.0 g/10 min
  • EPM Mooney viscosity: 25 ML 1+8 (127°C), and ethylene content: 70%.
  • maleic anhydride amount of the acid: 0.3%, referred to as CMPE 10 CMEPM 90).
  • Component E Acrylonitrile-butadiene copolymer rubber (having a Mooney viscosity of 56 ML 1+8 (100°C) and containing 35% of acrylonitrile, referred to as NBR hereinafter).
  • Component F Zinc oxide, zinc chloride, 2,5-di-(tbutylperoxy)-hexyne-3 (crosslinking agent, referred to as "P.o” hereinafter), and magnesium oxide (halogen capturing agent).
  • Component G Naphthenic and paraffinic mixed process oil (referred to as "softener” hereinafter), and talc (having an average particle diameter of 4 um).
  • component F crosslinking agent
  • component F crosslinking agent
  • Table 2 shows the characteristic properties of each composition.
  • the composition in Example 17 was examined for the degree of crosslinking.
  • the amount of insoluble matter (excluding talc) was 13.0%, and the infrared absorption spectrum indicated that crosslinking took place only in component B.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Composition et mise en oeuvre d'un élastomère thermoplastique comprenant une polyoléfine cristalline, du caoutchouc butyle halogéné, du caoutchouc copolymère oléfinique, de la polyoléfine modifiée avec notamment de l'anhydride maléique et éventuellement du caoutchouc nitrile, le caoutchouc butyle halogéné étant au moins partiellement réticulé par utilisation d'un oxyde et/ou d'un chlorure de métal, par exemple de l'oxyde de zinc. La réticulation se fait dans des conditions de mélange dynamiques et la composition qui en résulte présente une résistance, un rendement et des propriétés de mise en oeuvre supérieures. En outre, l'utilisation de caoutchouc nitrile confère à la composition une résistance aux huiles améliorée.
PCT/US1986/001306 1985-06-19 1986-06-16 Composition d'elastomere thermoplastique WO1986007600A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE8686904526T DE3673973D1 (de) 1985-06-19 1986-06-16 Thermoplastische elastomerzusammensetzungen.
BR8606735A BR8606735A (pt) 1985-06-19 1986-06-16 Composicao de elastomero termoplastico
KR1019870700143A KR920010646B1 (ko) 1985-06-19 1986-06-16 열가소성 엘라스토머 조성물 및 그 제조방법
NO870647A NO870647D0 (no) 1985-06-19 1987-02-18 Termoplastisk elastomersammensetning.
DK084687A DK84687A (da) 1985-06-19 1987-02-19 Termoplastisk elastomerkomposition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP131670/85 1985-06-19
JP131671/85 1985-06-19
JP13167185A JPS61291639A (ja) 1985-06-19 1985-06-19 熱可塑性エラストマ−組成物
JP60131670A JPS61291638A (ja) 1985-06-19 1985-06-19 熱可塑性エラストマ−組成物

Publications (1)

Publication Number Publication Date
WO1986007600A1 true WO1986007600A1 (fr) 1986-12-31

Family

ID=26466437

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1986/001306 WO1986007600A1 (fr) 1985-06-19 1986-06-16 Composition d'elastomere thermoplastique

Country Status (12)

Country Link
US (1) US4728692A (fr)
EP (1) EP0229156B1 (fr)
KR (1) KR920010646B1 (fr)
CN (1) CN1009104B (fr)
AU (1) AU599038B2 (fr)
BR (1) BR8606735A (fr)
CA (1) CA1265883A (fr)
DE (1) DE3673973D1 (fr)
DK (1) DK84687A (fr)
ES (1) ES8800968A1 (fr)
NZ (1) NZ216583A (fr)
WO (1) WO1986007600A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287282A1 (fr) * 1987-04-07 1988-10-19 Tonen Chemical Corporation Composition élastomère thermoplastique
EP0354685A1 (fr) * 1988-07-27 1990-02-14 Tonen Chemical Corporation Composition élastomère thermoplastique
WO1990014389A2 (fr) * 1989-05-26 1990-11-29 Advanced Elastomer Systems, L.P. Alliages dynamiquement vulcanises comportant deux copolymeres dans la phase reticulee ainsi qu'une matrice cristalline
EP0434458A2 (fr) * 1989-12-22 1991-06-26 Exxon Chemical Patents Inc. Elastomères réticulés partiellement et leur procédé de fabrication
EP0588029A1 (fr) * 1992-09-03 1994-03-23 RESINE SINTETICHE ADAMOLI S.p.A. Composition de polypropylène modifié, calandrable et soudable à haute fréquence
WO2014102500A1 (fr) * 2012-12-26 2014-07-03 Herakles Composition elastomere autoadherente
EP3662014B1 (fr) 2017-08-03 2023-01-04 Sika Technology AG Composition polymère présentant des propriétés mécaniques améliorées

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960830A (en) * 1984-07-11 1990-10-02 Exxon Research And Engineering Company Dynamically cured thermoplastic olefin polymers
JPS62201950A (ja) * 1986-03-03 1987-09-05 Toa Nenryo Kogyo Kk 熱可塑性エラストマ−組成物
US4802155A (en) * 1986-03-03 1989-01-31 Matsushita Electric Industrial Co., Ltd. Recording disc playback apparatus
CA1321850C (fr) * 1987-03-31 1993-08-31 John F. Aleckner, Jr. Composes de matieres thermoplastiques et articles fabriques avec ces composes
JPH0819281B2 (ja) * 1987-07-30 1996-02-28 三菱化学株式会社 吸水性樹脂組成物
US4810752A (en) * 1987-09-24 1989-03-07 The West Company Halobutyl thermoplastic elastomer
KR920003034B1 (ko) * 1988-06-21 1992-04-13 동양나이론 주식회사 열가소성 탄성중합체 수지조성물 및 그 제조방법
CA2011543A1 (fr) * 1989-03-09 1990-09-09 Keisaku Yamamoto Caoutchouc servant a la fabrication d'eponge et compositions a base de caoutchouc pour la fabrication d'eponge
US5043392A (en) * 1989-04-19 1991-08-27 Polysar Limited Toughened thermoplastics
US4921910A (en) * 1989-04-19 1990-05-01 Polysar Limited Toughened thermoplastics
US5157081A (en) * 1989-05-26 1992-10-20 Advanced Elastomer Systems, L.P. Dynamically vulcanized alloys having two copolymers in the crosslinked phase and a crystalline matrix
CA2023255A1 (fr) * 1989-12-15 1991-06-16 Narayanaswami R. Dharmarajan Alliages vulcanises par voie dynamique, adherant a des copolymeres de styrene et a des compositions de polyester
US5409779A (en) * 1991-02-07 1995-04-25 Cadillac Products, Inc. Shield for water and sound
US6045921A (en) 1991-02-07 2000-04-04 Cadillac Products, Inc. Shield for water and sound
KR950007662B1 (ko) * 1991-12-24 1995-07-14 주식회사럭키 우수한 도장성을 가진 올레핀계 수지 조성물
WO1997023561A1 (fr) * 1995-12-26 1997-07-03 Asahi Glass Company Ltd. Composition a base de resine pour materiaux de construction et panneaux a double vitrage
EP1149866A3 (fr) * 2000-04-27 2003-04-23 JSR Corporation Composition à base de particules de caoutchouc réticulées et de caoutchoucs non réticulés
WO2002049501A2 (fr) * 2000-12-18 2002-06-27 Board Of Regents, University Of Texas System Chimiotherapie et radiotherapie regionales locales au moyen d'un hydrogel in situ
US7291677B2 (en) * 2003-12-15 2007-11-06 Solvay Engineered Polymers, Inc. Adherent, modified thermoplastic elastomeric blends, articles, and methods
KR100705659B1 (ko) * 2005-01-17 2007-04-10 (주)폴리머스넷 아크릴레이트계 고분자 수지
KR100705656B1 (ko) * 2005-02-17 2007-04-10 (주)폴리머스넷 직접 도장이 가능한 폴리프로필렌계 복합소재 조성물
KR100690975B1 (ko) * 2005-02-24 2007-03-09 (주)폴리머스넷 표면 인쇄성이 향상된 폴리올레핀계 수지 조성물
US20070270538A1 (en) * 2006-05-19 2007-11-22 Marc Stacey Somers Elastomeric compositions comprising butyl rubber and propylene polymers
KR100866652B1 (ko) * 2007-05-18 2008-11-03 (주)폴리머스넷 폴리아크릴레이트계 고분자 수지
DE102016103823A1 (de) * 2016-03-03 2017-09-07 Kraiburg Tpe Gmbh & Co. Kg Thermoplastische Elastomerzusammensetzung aus einem Elastomer und einem nicht-elastomeren Polyolefin, das mit einem Anhydrid einer organischen Carbonsäure funktionalisiert ist
CN107501603A (zh) * 2017-08-02 2017-12-22 江苏道勤新材料科技有限公司 一种耐屈挠性高耐油再生橡胶的生产工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904470A (en) * 1973-05-02 1975-09-09 Mitsui Petrochemical Ind Method for bonding rubber to plastics
US4048261A (en) * 1975-11-10 1977-09-13 The B. F. Goodrich Company Vulcanizable compositions of a halogen-containing polymer and a diene-nitrile rubber having active halogen cure sites
US4130534A (en) * 1976-12-27 1978-12-19 Monsanto Company Elastoplastic compositions of butyl rubber and polyolefin resin
US4299931A (en) * 1980-03-10 1981-11-10 Monsanto Company Compatibilized polymer blends
JPS56159239A (en) * 1980-05-12 1981-12-08 Nippon Petrochem Co Ltd Modified polyolefin composition
US4409365A (en) * 1982-11-22 1983-10-11 Monsanto Company Thermoplastic rubber blends comprising crystalline polyolefin, vulcanized mono-olefin rubber and vulcanized nitrile rubber

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4593062A (en) * 1984-12-10 1986-06-03 Exxon Research & Engineering Co. Dynamically cured thermoplastic olefin polymers

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3904470A (en) * 1973-05-02 1975-09-09 Mitsui Petrochemical Ind Method for bonding rubber to plastics
US4048261A (en) * 1975-11-10 1977-09-13 The B. F. Goodrich Company Vulcanizable compositions of a halogen-containing polymer and a diene-nitrile rubber having active halogen cure sites
US4130534A (en) * 1976-12-27 1978-12-19 Monsanto Company Elastoplastic compositions of butyl rubber and polyolefin resin
US4299931A (en) * 1980-03-10 1981-11-10 Monsanto Company Compatibilized polymer blends
JPS56159239A (en) * 1980-05-12 1981-12-08 Nippon Petrochem Co Ltd Modified polyolefin composition
US4409365A (en) * 1982-11-22 1983-10-11 Monsanto Company Thermoplastic rubber blends comprising crystalline polyolefin, vulcanized mono-olefin rubber and vulcanized nitrile rubber

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0287282A1 (fr) * 1987-04-07 1988-10-19 Tonen Chemical Corporation Composition élastomère thermoplastique
WO1988008015A1 (fr) * 1987-04-07 1988-10-20 Exxon Chemical Patents, Inc. Composition elastomere thermoplastique
EP0354685A1 (fr) * 1988-07-27 1990-02-14 Tonen Chemical Corporation Composition élastomère thermoplastique
WO1990014389A2 (fr) * 1989-05-26 1990-11-29 Advanced Elastomer Systems, L.P. Alliages dynamiquement vulcanises comportant deux copolymeres dans la phase reticulee ainsi qu'une matrice cristalline
WO1990014389A3 (fr) * 1989-05-26 1991-10-31 Exxon Chemical Patents Inc Alliages dynamiquement vulcanises comportant deux copolymeres dans la phase reticulee ainsi qu'une matrice cristalline
EP0754726A2 (fr) * 1989-05-26 1997-01-22 Advanced Elastomer Systems, L.P. Alliages dynamiquement vulcanisés comportant deux copolymères dans la phase réticulée ainsi qu'une matrice cristalline
EP0754726A3 (fr) * 1989-05-26 1999-01-07 Advanced Elastomer Systems, L.P. Alliages dynamiquement vulcanisés comportant deux copolymères dans la phase réticulée ainsi qu'une matrice cristalline
EP0434458A2 (fr) * 1989-12-22 1991-06-26 Exxon Chemical Patents Inc. Elastomères réticulés partiellement et leur procédé de fabrication
EP0434458A3 (en) * 1989-12-22 1992-08-26 Exxon Chemical Patents Inc. Partially crosslinked elastomeric polymers and process for producing the same
EP0588029A1 (fr) * 1992-09-03 1994-03-23 RESINE SINTETICHE ADAMOLI S.p.A. Composition de polypropylène modifié, calandrable et soudable à haute fréquence
WO2014102500A1 (fr) * 2012-12-26 2014-07-03 Herakles Composition elastomere autoadherente
EP3662014B1 (fr) 2017-08-03 2023-01-04 Sika Technology AG Composition polymère présentant des propriétés mécaniques améliorées

Also Published As

Publication number Publication date
CN1009104B (zh) 1990-08-08
NZ216583A (en) 1989-10-27
KR920010646B1 (ko) 1992-12-12
US4728692A (en) 1988-03-01
EP0229156B1 (fr) 1990-09-05
AU6131586A (en) 1987-01-13
EP0229156A1 (fr) 1987-07-22
EP0229156A4 (fr) 1987-11-23
BR8606735A (pt) 1987-08-11
KR880700017A (ko) 1988-02-15
DE3673973D1 (de) 1990-10-11
DK84687D0 (da) 1987-02-19
AU599038B2 (en) 1990-07-12
CA1265883A (fr) 1990-02-13
ES8800968A1 (es) 1987-12-01
CN86105629A (zh) 1987-05-27
DK84687A (da) 1987-02-19
ES556204A0 (es) 1987-12-01

Similar Documents

Publication Publication Date Title
EP0229156B1 (fr) Composition d'elastomere thermoplastique
JP2610426B2 (ja) 熱可塑性エラストマー組成物
US5621045A (en) Thermoplastic vulcanizates from isobutylene rubber and either EPDM or a conjugated diene rubber
US5157081A (en) Dynamically vulcanized alloys having two copolymers in the crosslinked phase and a crystalline matrix
EP0738756B1 (fr) Composition à base d'élastomère thermoplastique
EP0404351A2 (fr) Mélanges vulcanisés dynamiquement présentant un équilibre entre rigidité et résistance au choc
AU598808B2 (en) Thermoplastic elastomer composition
CA2233904A1 (fr) Vulcanisat d'elastomere thermoplastique
JPH05222214A (ja) 防水シート
EP0354685B1 (fr) Composition élastomère thermoplastique
JP3445314B2 (ja) オレフィン系熱可塑性エラストマー組成物
JPH0564662B2 (fr)
JP2691172B2 (ja) 耐侯性に優れた熱可塑性エラストマー組成物
JP3535640B2 (ja) 熱可塑性エラストマー組成物
JPH0770380A (ja) オレフィン系熱可塑性エラストマー
JPH0564661B2 (fr)
JPH0576973B2 (fr)
JPS61291638A (ja) 熱可塑性エラストマ−組成物
JPS61291639A (ja) 熱可塑性エラストマ−組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR DK KR NO SU US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL SE

WWE Wipo information: entry into national phase

Ref document number: 1986904526

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1986904526

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1986904526

Country of ref document: EP